CN105536757A - Method for preparing high-activity nano-mesoporous SiO2-TiO2 composite photocatalytic material - Google Patents
Method for preparing high-activity nano-mesoporous SiO2-TiO2 composite photocatalytic material Download PDFInfo
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- CN105536757A CN105536757A CN201610056114.7A CN201610056114A CN105536757A CN 105536757 A CN105536757 A CN 105536757A CN 201610056114 A CN201610056114 A CN 201610056114A CN 105536757 A CN105536757 A CN 105536757A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000000694 effects Effects 0.000 title claims description 10
- 230000001699 photocatalysis Effects 0.000 title abstract description 6
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000011941 photocatalyst Substances 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 21
- 239000004408 titanium dioxide Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- -1 silane compound Chemical class 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000003916 acid precipitation Methods 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005314 correlation function Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- FMLYSTGQBVZCGN-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Si+2]=O.[O-2].[O-2] FMLYSTGQBVZCGN-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- SOBXOQKKUVQETK-UHFFFAOYSA-H titanium(3+);trisulfate Chemical compound [Ti+3].[Ti+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SOBXOQKKUVQETK-UHFFFAOYSA-H 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a nano-mesoporous SiO2-TiO2 composite photocatalytic material. The method is simple in process, high in operability, low in cost and suitable for large-scale preparation, has the possibility of industrial production and has wide application prospects. Besides, the method has another advantage that in a whole reaction system, only water serves as a solvent, other organic solvents like alcohol are not used, accordingly pollution to the environment is effectively reduced, and safety of a production link is improved.
Description
Technical field
The invention belongs to inorganic, metal oxide preparation field, the preparation method of particularly nano meso-porous titanium dioxide/silica composite photocatalyst material.
Background technology
Nano-TiO
2as functional inorganic material, be with a wide range of applications at numerous areas such as coating, opto-electronic conversion, catalysis, function ceramics, anti-biotic materials, its synthesis and application study are the emphasis of correlation function Material Field research always.This wherein, be a kind of emerging green technology effectively removing chemical pollutant using nano-titanium oxide as the Photocatalitic Technique of Semiconductor of photochemical catalyst, it can accelerate the degradation process of oxynitrides and sulfide.Namely the hole utilizing solid semiconductor catalysis material to produce by optical excitation, captures NO
xelectronics in system, makes it activate and be oxidized to NO
3 -stay catalyst surface, thus the NO of solidification haze
xsource.At road traffic space application photocatalytic degradation material, modification is carried out as utilized catalysis material road pavement material, or produce coating by catalysis material, what can make road paint, road equipment material possesses harmful substance in degrading tail gas, reducing tail gas to the pollution effects of air, is the effective ways of the end treatment of moving source tail gas clean-up.
But conductor photocatalysis is by NO
xbe oxidized to NO
3 -reaction, through many intermediate steps, have some harmful intermediate products and generate, the NO as part is oxidized to NO
2, and be released, this is harmful to environment, can promote the formation of photochemical fog.And photocatalysis technology and adsorption technology are combined, be the primary solutions addressed this problem.High-absorption material is to NO and NO
2absorption, makes the NO generated through Photocatalytic Oxidation With Semiconductors NO
2namely also NO is oxidized to further by absorption in the moment produced
3 -, thus avoid intermediate product NO
2release.
At present, for mainly comprising the material such as active carbon, molecular sieve with the high adsorption material of nano-titanium oxide compound, but absorbent charcoal material is due to light tight, lower to the utilization rate of load catalysis material.And adopt molecular sieve as carrier, there is cost higher, back loading technique is easy to the problem of blocking pipe simultaneously.Therefore, direct synthesized high-performance nano silicon oxide-titanium oxide composite photocatalyst material has important Research Significance.At present, associated materials synthetic method generally adopts respectively synthetic silica and titania meterial, then the technique of compound, and step is numerous and diverse, and there is subsequent oxidation silicon and titanium oxide cannot the problem of effective compound.Its main cause is, titanium oxide crystallization needs high temperature sintering usually, and silica generally can in liquid phase direct hydrolysis, and therefore, liquid phase is directly synthesized composite construction and had difficulties.
Summary of the invention
According to an aspect of the present invention, one object of the present invention is to provide a kind of simple and easy to control, respond well, and the one kettle way being suitable for large-scale industrial production prepares the mesoporous SiO of high-activity nano
2-TiO
2the method of composite photocatalyst material.
In order to realize above-mentioned purpose of the present invention, the preparation method of nano meso-porous titanium dioxide of the present invention/silica composite photocatalyst material comprises the following steps:
1) controlled hydrolysis prepares ortho-titanic acid precipitation
Inorganic base or inorganic acid are joined containing Ti
4+ion concentration is in the titanium liquid of 0.01 ~ 0.50mol/L, and the pH value making titanium liquid is 5 ~ 11, obtains ortho-titanic acid precipitation, the precipitation obtained purified process removing impurity.
2) hydrogen peroxide-ammino-complex preparation
Hydrogenperoxide steam generator dispersion steps 1 with mass percentage concentration is 10% to 60%) the compound ortho-titanic acid that obtains precipitates into solution state, wherein H
2o
2control 1 to 25 with the molecule mol ratio of Ti; In obtained titanium peroxide solution, add ammonium hydrate, form titanium-peroxidating-ammonia Compound complex solution, wherein NH
4 +control 1 to 25 with the molecule mol ratio of Ti.
3) nano meso-porous titanium dioxide/silica composite photocatalyst material is prepared
It is 0 ~ 100 DEG C in reaction temperature, preferably 10 ~ 90 DEG C, under being more preferably 60 ~ 80 DEG C of stirrings, to step 2) add organic silane compound in titanium-peroxidating-ammonia Compound complex solution of preparing and react, wherein, the volume ratio of organic silane compound and titanium-peroxidating-ammonia Compound complex solution is 10: 1 to 1: 10, heat time controls between 0.5 hour to 12 hours, between being preferably 1 hour to 8 hours, be more preferably between 3 hours to 6 hours, after having reacted, through filtering, washing, drying waits post-processing step, obtain nano meso-porous titanium dioxide/silica composite photocatalyst material.
Wherein, step 1) in titanium liquid in Ti
4+ion concentration is for being preferably 0.1 ~ 0.3mol/L, more preferably 0.2 ~ 0.3mol/L.Described inorganic base is selected from least one in the group of sodium carbonate, sodium acid carbonate, potash, saleratus, NaOH, potassium hydroxide, ammoniacal liquor alkali electroless reagent place composition, be preferably NaOH, potassium hydroxide or ammoniacal liquor, described inorganic acid is selected from least one in the group that nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid forms, and is preferably nitric acid or hydrochloric acid.
Step 1) in titanium liquid source can pass through acidolysis ilmenite; Acidolysis metatitanic acid compounds; The dilution of titanium tetrachloride; Or the conventional method such as titanium sulfate, titanium sesquisulfate or titanyl sulfate hydrolysis obtains.Described purge process can by method removing impurity such as frozen recrystallizations.
Step 2) in the mass percentage concentration of hydrogenperoxide steam generator be preferably 20% to 40%, be more preferably 30%; H
2o
2preferably control 1 to 25 with the molecule mol ratio of Ti, be preferably 5 to 10; The mass percentage concentration of described ammonium hydrate is 0.1% to 10%, is preferably 1% to 6%, is more preferably 2% to 8%.NH
4 +preferably control 5 to 20 with the molecule mol ratio of Ti.Described ammonium hydrate is preferably ammoniacal liquor, ammonium chloride etc.
Step 3) in described organic silane compound structure be RR
1r
2r
3si; Wherein: R is C
1~ C
18oxyalkyl chain, R
1, R
2, R
3independently be selected from C
1~ C
18one in oxyalkyl chain, chlorine, amino, sulfonic group, wherein said C
1~ C
18oxyalkyl chain is preferably C
2~ C
8oxyalkyl chain, is more preferably C
3~ C
6oxyalkyl chain, more specifically, described organic silane compound can be four own TMOSs, four butoxy silanes, triethoxy chloro silane etc.
According to an aspect of the present invention, one object of the present invention is to provide a kind of high-activity nano mesoporous SiO
2-TiO
2composite photocatalyst material, described composite photocatalyst material is prepared by above method.
According to an aspect of the present invention, one object of the present invention is to provide a kind of coating, described in comprise according to mesoporous nano SiO of the present invention
2-TiO
2composite photocatalyst material, and other conventional paint ingredient, such as resin, antiseptic, levelling agent, pigment etc., as long as described conventional paint ingredient can not to described mesoporous nano SiO
2-TiO
2the catalytic performance of composite photocatalyst material causes adverse effect.Coating according to the present invention can adopt the modes such as spraying, roller coating, brushing directly to apply in addition.
Beneficial effect
The present invention is compared with the preparation method of bibliographical information, and method flow of the present invention is simple, workable, simultaneously less expensive, is applicable to batch preparation, possesses the possibility of suitability for industrialized production, be with a wide range of applications.Another considerable advantage of the present invention is that whole reaction system all only uses water as solvent in addition, and not with an organic solvent, such as alcohol etc., thus efficiently reduce the pollution to environment, improve the security of production link.
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b are respectively the transmission electron microscope picture of the nano meso-porous titanium dioxide/silica composite photocatalyst material prepared by the embodiment of the present invention 1.
Fig. 2 a, Fig. 2 b are respectively nano meso-porous titanium dioxide/silica composite photocatalyst material ESEM (SEM) analysis result prepared by the embodiment of the present invention 1.
The specific area that Fig. 3 is the nano meso-porous titanium dioxide prepared by the embodiment of the present invention 2/silica composite photocatalyst material and mesopore size result.
Fig. 4 is the photocatalysis result of the nano meso-porous titanium dioxide prepared by the embodiment of the present invention 3/silica composite photocatalyst material.
Detailed description of the invention
The present invention mainly utilizes the water-based complex formed by water-soluble titanium peroxide precursor and ammonia complexing, catalysis organic silane compound forms silica with great specific surface area at titanium peroxide surface hydrolysis, further heat treatment makes titanium per-compound crystallization subsequently, thus forms the mesoporous SiO of high-activity nano based on one kettle way technique
2-TiO
2composite photocatalyst material.
Coating according to the present invention may be used for the substrate surfaces such as outdoor and indoor wall, ground, brick face and strong adhesion.Such as can by coatings according to the present invention on the surface of floor tile, for outdoor road surfacing; Or after freeway guardrail dope lacquerer sequence completes, described coating is directly coated on skin of paint, thus realizes the NO to air middle and high concentration
xdecompose.And also can directly be coated on the surface of external wall according to coating of the present invention, effectively realize pollutants in air (NO
x, SO
x, VOCs etc.) degraded and the small particles of pollution thing absorption such as PM2.5.
Following examples are only enumerate as the example of embodiment of the present invention, do not form any restriction to the present invention, it will be appreciated by those skilled in the art that the amendment in the scope not departing from essence of the present invention and design all falls into protection scope of the present invention.
Hereinafter, describe in detail with reference to the accompanying drawings preferred embodiment of the present disclosure.Before described, the term used in description and claims should be understood, and should not be construed as and be confined to general and dictionary meaning, but the principle of term suitably should be defined based on allowing the artificially best explanation of invention, make an explanation based on the meaning and concept corresponding to the technology of the present invention aspect.Therefore, at this description only preferred embodiment for the purpose of illustration, and be not mean to limit the scope of the invention, it is therefore to be understood that, can be made other equivalently to implement and amendment under without departing from the spirit and scope of the present invention.
Embodiment 1
First use 500ml deionized water dissolving 100g titanyl sulfate, obtain aqueous solution of titanyle sulfate; By mass concentration be 36% ammonia water titration titanyl sulfate solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain ortho-titanic acid.Dissolving 5g ortho-titanic acid with the aqueous hydrogen peroxide solution that 5ml mass percentage concentration is 30% and obtain the titanium peroxide aqueous solution, is that the pH of the adjusted titanium oxide aqueous solution of ammoniacal liquor of 2.5% is about 10 by mass percentage concentration; At temperature is 80 DEG C, add the four own TMOSs that 5ml mass percentage concentration is 28%, mechanical agitation back flow reaction 4 hours, after having reacted, product is through filtering, washing, and drying waits process to obtain nano meso-porous titanium dioxide/silica composite photocatalyst material.Fig. 1 a, Fig. 1 b are respectively the transmission electron microscope picture of the nano meso-porous titanium dioxide/silica composite photocatalyst material prepared by the present embodiment, and Fig. 2 a, Fig. 2 b are respectively the nano meso-porous titanium dioxide/silica composite photocatalyst material sem analysis result prepared by the present embodiment.As can be seen from the figure, have good degree of crystallization according to titania/silica composite prepared by the present embodiment, define meso-hole structure simultaneously, this structure is conducive to catalytic applications.
Embodiment 2
With 500ml deionized water dissolving 100g titanyl sulfate, obtain aqueous solution of titanyle sulfate; By mass concentration be 36% ammonia water titration titanyl sulfate solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain ortho-titanic acid.Dissolving 10g ortho-titanic acid with the aqueous hydrogen peroxide solution that 10ml mass percentage concentration is 30% and obtain the titanium peroxide aqueous solution, is that the pH of the adjusted titanium oxide aqueous solution of ammoniacal liquor of 2.5% is about 5 by mass percentage concentration; At temperature is 50 DEG C, add four butoxy silanes that 5ml mass percentage concentration is 28%, mechanical agitation back flow reaction 12 hours, after having reacted, product is through filtering, washing, and drying waits process to obtain nano meso-porous titanium dioxide/silica composite photocatalyst material.The specific area of gained nano meso-porous titanium dioxide/silica composite photocatalyst material and mesopore size analysis result are see Fig. 3, and specific area is 347.028m
2/ g, average diameter is 9.8nm, confirms that the composite obtained is mesoporous nano structure.
Embodiment 3
With 500ml deionized water dissolving 100g titanyl sulfate, obtain aqueous solution of titanyle sulfate; By mass concentration be 36% ammonia water titration titanyl sulfate solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain ortho-titanic acid.Dissolving 5g ortho-titanic acid with the aqueous hydrogen peroxide solution that 5ml mass percentage concentration is 30% and obtain the titanium peroxide aqueous solution, is that the pH of the adjusted titanium oxide aqueous solution of ammoniacal liquor of 2.5% is about 7 by mass percentage concentration; At temperature is 80 ~ 100 DEG C, add the four own TMOSs that 5ml mass percentage concentration is 28%, mechanical agitation back flow reaction 4 hours, after having reacted, product is through filtering, washing, and drying waits process to obtain nano meso-porous titanium dioxide/silica composite photocatalyst material.
EXPERIMENTAL EXAMPLE: NO
xdegradation experiment
The composite titania/silica photocatalyst material obtained is carried out NO
xdegradation experiment, described experiment is carried out as follows:
Be coated on the glass plate of 10cm × 20cm by the nano meso-porous titanium dioxide prepared according to embodiment 3/silica composite photocatalyst material, the consumption of described catalysis material is 0.5g, then with 10 μ w/cm
2ultraviolet light light intensity when irradiating, flow through this glass plate with the air-flow of NO containing 1ppm, gas flow rate is 800ml/min.Adopt commercially available titanium dioxide (P25) (Germany wins wound industrial group EVONIK for Degussa Degussa, content: 99.8%) as catalyst or not coated catalysts in addition, do same experiment as a comparison.
As can be seen from the result of Fig. 4, when not using catalyst, the NO in gas
xsubstantially without degraded.And have employed according to composite titania/silica photocatalyst material of the present invention, NO
xdegradation rate can reach 96%, comparatively speaking, adopt commercially available titanium dioxide to NO
xdegradation rate be 92%.
Claims (10)
1. the mesoporous SiO of high-activity nano
2-TiO
2the preparation method of composite photocatalyst material, said method comprising the steps of:
1) controlled hydrolysis prepares ortho-titanic acid precipitation
Inorganic base or inorganic acid are joined containing Ti
4+ion concentration is in the titanium liquid of 0.01 ~ 0.50mol/L, and the pH value making titanium liquid is 5 ~ 11, obtains ortho-titanic acid precipitation, the precipitation obtained purified process removing impurity;
2) hydrogen peroxide-ammino-complex preparation
Hydrogenperoxide steam generator dispersion steps 1 with mass percentage concentration is 10% to 60%) the compound ortho-titanic acid that obtains precipitates into solution state, wherein H
2o
2control 1 to 25 with the molecule mol ratio of Ti; In obtained titanium peroxide solution, add ammonium hydrate, form titanium-peroxidating-ammonia Compound complex solution, wherein NH
4 +control 1 to 25 with the molecule mol ratio of Ti;
3) nano meso-porous titanium dioxide/silica composite photocatalyst material is prepared
Under reaction temperature is 0 ~ 100 DEG C of stirring, to step 2) add organic silane compound in titanium-peroxidating-ammonia Compound complex solution of preparing and react, wherein, the volume ratio of organic silane compound and titanium-peroxidating-ammonia Compound complex solution is 10: 1 to 1: 10, heat time controls between 0.5 hour to 12 hours, after having reacted, through post-processing steps such as filtering, wash, be dry, obtain nano meso-porous titanium dioxide/silica composite photocatalyst material.
2. preparation method according to claim 1, is characterized in that, step 3) in reaction temperature be 10 ~ 90 DEG C, be preferably 60 ~ 80 DEG C, the heat time controls between 1 hour to 8 hours, is preferably between 3 hours to 6 hours.
3. preparation method according to claim 1, is characterized in that, step 1) described in Ti in titanium liquid
4+ion concentration is 0.1 ~ 0.3mol/L, is preferably 0.2 ~ 0.3mol/L; Described inorganic base is selected from least one in the group of sodium carbonate, sodium acid carbonate, potash, saleratus, NaOH, potassium hydroxide, ammoniacal liquor alkali electroless reagent place composition, is preferably NaOH, potassium hydroxide or ammoniacal liquor; Described inorganic acid is selected from least one in the group that nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid forms, and is preferably nitric acid or hydrochloric acid.
4. preparation method according to claim 3, is characterized in that, described inorganic base is selected from NaOH, potassium hydroxide or ammoniacal liquor, and described inorganic acid is selected from nitric acid or hydrochloric acid.
5. preparation method according to claim 1, is characterized in that, step 2) in the mass percentage concentration of hydrogenperoxide steam generator be 20% to 40%; H
2o
2preferably control 1 to 25 with the molecule mol ratio of Ti; The mass percentage concentration of described ammonium hydrate is 0.1% to 10%; NH
4 +preferably control 5 to 20 with the molecule mol ratio of Ti.Described ammonium hydrate is ammoniacal liquor or ammonium chloride.
6. preparation method according to claim 1, is characterized in that, step 2) in the mass percentage concentration of hydrogenperoxide steam generator be 30%; H
2o
2preferably control 5 to 10 with the molecule mol ratio of Ti; The mass percentage concentration of described ammonium hydrate is 1% to 6%, is preferably 2% to 8%.
7. preparation method according to claim 1, is characterized in that, step 3) in described organic silane compound structure be RR
1r
2r
3si; Wherein: R is C
1~ C
18oxyalkyl chain, R
1, R
2, R
3independently be selected from C
1~ C
18one in oxyalkyl chain, chlorine, amino, sulfonic group, wherein said C
1~ C
18oxyalkyl chain is preferably C
2~ C
8oxyalkyl chain, is more preferably C
3~ C
6oxyalkyl chain, more specifically, described organic silane compound can be four own TMOSs, four butoxy silanes, triethoxy chloro silane etc.
8. the mesoporous SiO of high-activity nano
2-TiO
2composite photocatalyst material, described composite photocatalyst material is prepared by the method in claim 1 to 7 described in any one.
9. a coating, it comprises the mesoporous SiO of high-activity nano according to claim 8
2-TiO
2composite photocatalyst material, and other conventional paint ingredient.
10. coating according to claim 9, is characterized in that, described conventional paint ingredient comprises resin, antiseptic, levelling agent and/or pigment.
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| CN109225186A (en) * | 2018-10-11 | 2019-01-18 | 南京工业大学 | Titanium dioxide and silicon dioxide composite material catalyst and preparation and application |
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| CN112625471A (en) * | 2019-10-09 | 2021-04-09 | 任清扬 | Preparation method of photosensitive protection type titanium dioxide coating |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107890862A (en) * | 2017-11-10 | 2018-04-10 | 纳琦环保科技有限公司 | The preparation method of hollow structure titanium oxide/silica composite photocatalyst material |
| CN108355401A (en) * | 2018-02-09 | 2018-08-03 | 纳琦环保科技有限公司 | A kind of preparation method of novel inorganic porous purification filter core |
| CN110366444A (en) * | 2018-02-09 | 2019-10-22 | 纳琦环保科技有限公司 | A kind of synthetic method of the composite photocatalyst material with photo-thermal synergistic effect |
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| CN110366444B (en) * | 2018-02-09 | 2022-04-26 | 纳琦环保科技有限公司 | Synthetic method of composite photocatalytic material with photo-thermal synergistic effect |
| CN109225186A (en) * | 2018-10-11 | 2019-01-18 | 南京工业大学 | Titanium dioxide and silicon dioxide composite material catalyst and preparation and application |
| CN109225186B (en) * | 2018-10-11 | 2021-10-08 | 南京工业大学 | Titanium dioxide and silicon dioxide composite material catalyst, preparation and application |
| CN112625471A (en) * | 2019-10-09 | 2021-04-09 | 任清扬 | Preparation method of photosensitive protection type titanium dioxide coating |
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